EP3730554A1 - Corps moulé réticulé, et procédé de fabrication de celui-ci - Google Patents

Corps moulé réticulé, et procédé de fabrication de celui-ci Download PDF

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Publication number
EP3730554A1
EP3730554A1 EP18892394.0A EP18892394A EP3730554A1 EP 3730554 A1 EP3730554 A1 EP 3730554A1 EP 18892394 A EP18892394 A EP 18892394A EP 3730554 A1 EP3730554 A1 EP 3730554A1
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EP
European Patent Office
Prior art keywords
molded article
conjugated polyene
crosslinking
ethylene
olefin
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EP18892394.0A
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German (de)
English (en)
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EP3730554A4 (fr
Inventor
Tatsuya Sakai
Ryohei SAEKI
Kiyohide Inomata
Yoshiharu Kikuchi
Kotaro Ichino
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Publication of EP3730554A1 publication Critical patent/EP3730554A1/fr
Publication of EP3730554A4 publication Critical patent/EP3730554A4/fr
Pending legal-status Critical Current

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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/247—Heating methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/0222—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould the curing continuing after removal from the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/02—Elements
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
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    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2019/00—Use of rubber not provided for in a single one of main groups B29K2007/00 - B29K2011/00, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0014—Catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0041—Anti-odorant agents, e.g. active carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
    • B29K2105/243—Partially cured
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/05—Polysiloxanes containing silicon bound to hydrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

  • the present invention relates to a method for producing, through two-stage crosslinking, a crosslinked molded article which includes a composition containing a polymer having a terminal double bond, preferably a composition containing an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer.
  • Copolymer compositions of Patent Literature 1 obtained by hydrosilyl-crosslinking an ethylene/ ⁇ -olefin/non-conjugated polyene random copolymer (hereinafter, sometimes abbreviated as EPDM) are superior in mechanical strength, heat aging resistance, compression set and bloom property to those obtained by sulfur vulcanization and peroxide crosslinking, and have characteristics such that continuous crosslinking is possible, and application of the copolymer compositions to seal components such as packings and gaskets is expected.
  • EPDM ethylene/ ⁇ -olefin/non-conjugated polyene random copolymer
  • the rubber composition described in Patent Literature 1 when used, it is difficult to obtain a crosslinked molded article by injection molding for the following reasons: the rubber composition has a short scorch time and a low crosslinking rate, and therefore use of an injection molding machine to obtain a crosslinked molded article leads to deterioration of processability in extrusion and injection molding due to, for example, the start of crosslinking in the injection molding machine; and it is necessary to hold a molded material in a mold for a relatively long time in order to perform crosslinking.
  • Patent Literature 1 Japanese Patent Laid-Open No. 2006-290917
  • the present invention provides a method for producing a crosslinked molded article by injection molding, the method enabling shortening of one cycle in injection molding and production of a crosslinked molded article having a lower compression set; and a crosslinked molded article having a lower compression set.
  • the present inventors have found that the above-described problems can be solved by combining a polymer having a terminal double bond so that excellent curing properties are exhibited when crosslinking is performed, preferably an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer described in this application, a crosslinking agent excellent in control of a crosslinking behavior as described in the present application, and a two-stage crosslinking method.
  • the present invention relates to the following items [1] to [6].
  • the molding time (one cycle) in injection molding of a crosslinked molded article can be shortened, and a crosslinked molded article having a lower compression set can be provided.
  • the method for producing a crosslinked molded article according to the present invention includes melt-kneading a polymer composition containing polymer having a terminal double bond, preferably an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S), a hydrosilyl group-containing compound (Y) having at least two hydrosilyl groups per molecule, a platinum-based catalyst (Z) for hydrosilicon crosslinking, and a reaction inhibitor (D), subjecting the polymer composition to injection molding in a mold, performing crosslinking in the mold for a short time, and then performing crosslinking in a heat medium.
  • S ethylene/ ⁇ -olefin/non-conjugated polyene copolymer
  • Y hydrosilyl group-containing compound having at least two hydrosilyl groups per molecule
  • Z platinum-based catalyst
  • D reaction inhibitor
  • the polymer usable in the method for producing a molded article according to the present invention may be used without being limited as long as the polymer has a terminal double bond, and in particular, the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) described below is preferable.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) to be used in the method for producing an article according to the present invention has structural units derived from ethylene (A), an ⁇ -olefin (B) having 3 to 20 carbon atoms, and a non-conjugated polyene (C) containing per molecule a total of two or more partial structures each selected from the group consisting of the structures of the following general formulae (I) and (II).
  • Such an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) may have, in addition to the structural units derived from the compounds (A), (B) and (C), structural units derived from a non-conjugated polyene (D) containing per molecule only one partial structure selected from the group consisting of the structures of the above general formulae (I) and (II).
  • Examples of the ⁇ -olefin (B) having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosen.
  • ⁇ -olefins having 3 to 8 carbon atoms, such as propylene, 1-butene, 1-hexene and 1-octene are preferable, with propylene being especially preferable.
  • ⁇ -olefins are preferable because the raw material cost is relatively low, the resulting ethylene/ ⁇ -olefin/non-conjugated polyene copolymer has excellent mechanical properties, and furthermore a molded article having rubber elasticity can be obtained.
  • These ⁇ -olefins may be used singly or in combination of the two or more kinds.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) contains structural units derived from at least one ⁇ -olefin (B) having 3 to 20 carbon atoms, and may contain structural units derived from two or more ⁇ -olefins (B) having 3 to 20 carbon atoms.
  • non-conjugated polyene (C) containing per molecule a total of two or more partial structures each selected from the group consisting of the structures of the above general formulae (I) and (II) include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene and dicyclopentadiene.
  • VNB 5-vinyl-2-norbornene
  • the non-conjugated polyene (C) includes VNB among the above-mentioned compounds because of high accessibility, good hydrosilyl crosslinking reactivity and high possibility of improving the heat resistance of the polymer composition. More preferably, the non-conjugated polyene (C) is VNB.
  • the non-conjugated polyene (C) may be used singly or in combination of the two or more kinds.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) of the present invention may contain, structural units derived from the non-conjugated polyene (D) containing per molecule only one partial structure selected from the group consisting of the structures of the above general formulae (I) and (II).
  • non-conjugated polyene (D) examples include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, 5-(2-ethyl-3-butenyl)-2-norbornene, 5-(6-heptenyl)-2-norbornene, 5-(3-methyl-5-hexenyl)-2-norbornene
  • ENB is preferable because of high accessibility, easy control of the crosslinking rate during hydrosilyl crosslinking and high possibility of obtaining good mechanical properties.
  • the non-conjugated polyenes (D) may be used singly or in combination of the two or more kinds.
  • the ratio of the structural units is not particularly limited as long as the purpose of the present invention is not hindered, and the ratio of the structural units is typically about 0 to 20 wt%, preferably about 0 to 8 wt%, more preferably about 0.01 to 8 wt% in terms of a weight fraction (where the total weight fraction of compounds (A), (B), (C) and (D) is 100 wt%).
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) is a copolymer having structural units derived from ethylene (A), an ⁇ -olefin (B) having 3 to 20 carbon atoms, the non-conjugated polyene (C), and optionally the non-conjugated polyene (D), and satisfies the following requirements (i) to (v) .
  • a-olefin having 3 to 20 carbon atoms is also referred to simply as an "a-olefin”.
  • the requirement (i) according to the present invention specifies that the molar ratio of ethylene/ ⁇ -olefin in the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) is from 40/60 to 99.9/0.1, and the molar ratio is preferably from 50/50 to 90/10, more preferably from 55/45 to 85/15, still more preferably from 55/45 to 78/22.
  • Such an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer according to the present invention is preferable because a molded article obtained by hydrosilyl crosslinking has excellent rubber elasticity, and is excellent in mechanical strength and flexibility.
  • the amount of ethylene (content of structural units derived from ethylene (A)) and the amount of the ⁇ -olefin (content of structural units derived from the ⁇ -olefin (B)) in the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) can be determined by 13 C-NMR.
  • the requirement (ii) specifies that in the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention, the weight fraction of structural units derived from the non-conjugated polyene (C) is in the range of 0.07 wt% to 10 wt% based on 100 wt% of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) (i.e. based on 100 wt% of the total weight fraction of all structural units).
  • the weight fraction of structural units derived from the non-conjugated polyene (C) is preferably 0.1 wt% to 8.0 wt%, more preferably 0.5 wt% to 5.0 wt%.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention satisfy the requirement (ii) because the crosslinked molded article according to the present invention has a sufficient hardness, and is excellent in mechanical properties, and when hydrosilyl crosslinking is performed, a high crosslinking rate is exhibited, and the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention becomes suitable for production of a crosslinked molded article.
  • the amount of the non-conjugated polyene (C) (content of structural units derived from the non-conjugated polyene (C)) in the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) can be determined by 13 C-NMR.
  • the requirement (iii) specifies that in the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention, the weight average molecular weight (Mw) of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer, the weight fraction of structural units derived from the non-conjugated polyene (C) (weight fraction of (C): wt%) in the copolymer, and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following relational Formula (1).
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention satisfy the requirement (iii) because the content of structural units derived from the non-conjugated polyene (C) such as VNB is appropriate, and sufficient hydrosilyl crosslinking performance is exhibited, and when a crosslinked molded article is produced using the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer composition according to the present invention, an excellent crosslinking rate is exhibited, and the molded article after crosslinking has excellent mechanical properties.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention satisfies the following relational Formula (1'). 4.5 ⁇ Mw ⁇ weight fraction of C / 100 / molecular weight of C ⁇ 35
  • the weight average molecular weight (Mw) of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) can be determined as a polystyrene equivalent value measured gel permeation chromatography (GPC).
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) has an appropriate crosslinking degree when the value of "Mw ⁇ weight fraction of (C)/100/molecular weight of (C)" satisfies the Formula (1) or (1'), and use of the copolymer enables production of a molded article having excellent and well-balanced mechanical properties and heat aging resistance.
  • the number of long-chain branches increases as the content of structural units derived from the non-conjugated polyene increases, but it is considered that the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention can satisfy the Formula (2) because there is a smaller number of long-chain branches as compared to a known ethylene/ ⁇ -olefin/non-conjugated polyene copolymer.
  • the P value is a ratio ( ⁇ *ratio) determined from a complex viscosity at 0.1 rad/s and a complex viscosity at 100 rad/s, where the complex viscosities are determined by performing measurement under the condition of 190°C, a strain of 1.0% and different frequencies using a viscoelasticity measuring apparatus (Ares manufactured by Rheometric Scientific, Inc.).
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) satisfies the following Formula (2').
  • the intrinsic viscosity [ ⁇ ] is a value measured in decalin at 135°C.
  • the requirement (v) specifies that in the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention, the number of long-chain branches per 1000 carbon atoms (LCB 1000C ) which is obtained using 3D-GPC, and the natural logarithm of the weight average molecular weight (Mw) represented by [Ln (Mw)] satisfy the following Formula (3).
  • the above Formula (3) specifies the upper limit of the content of long-chain branches per unit number of carbon atoms in the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S).
  • Such an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) is preferable because the ratio of long-chain branches contained is low, excellent curing properties are exhibited when hydrosilyl crosslinking is performed, and a molded article obtained using the copolymer is excellent in heat aging resistance.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention satisfies the following Formula (3').
  • the molecular weight (Mw) and the number of long-chain branches per 1000 carbon atoms (LCB 1000C ) can be determined by a structural analysis method using 3D-GPC.
  • Mw and LCB 1000C are determined in the following manner.
  • the absolute molecular weight distribution is determined using a 3D-high-temperature GPC apparatus (Model PL-GPC220 manufactured by Polymer Laboratories Ltd.), and simultaneously, the intrinsic viscosity is determined with a viscometer.
  • Basic measurement conditions are as follows.
  • the dn/dc value necessary for determination of the absolute molecular weight is determined for each sample from the dn/dc value (0.053) of standard polystyrene (molecular weight: 190000) and the response intensity of the differential refractometer per unit injection mass.
  • the averages are calculated as g' from the following formulae (v-2), (v-3) and (v-4).
  • the trendline based on which the ith slice component has only short-chain branch structures is determined for each sample.
  • Number average long-chain branch parameter g ′ n ⁇ C i / M i ⁇ g ′ i ⁇ C i / M i
  • the number of branch points per molecular chain (BrNo), the number of long-chain branches per 1000 carbon atoms (LCB 1000C ) and the branching degree per unit molecular weight ( ⁇ ) are calculated with the parameter g'w.
  • the value of BrNo is calculated from the Zimm-Stockmayer formula (v-5), and the values of LCB 1000C and ⁇ are calculated from formulae (v-6) and (v-7).
  • the parameter g is a long-chain branch parameter determined from the radius of inertia (Rg), and there is the following simple correlation between the parameter g and the parameter g' determined from the intrinsic viscosity. For ⁇ in the fromula, various values have been proposed depending on shapes of molecules.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention has an intrinsic viscosity [ ⁇ ] of preferably 0.1 to 5 dL/g, more preferably 0.5 to 5.0 dL/g, still more preferably 0.9 to 4.0 dL/g.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention has a weight average molecular weight (Mw) of preferably 10,000 to 600,000, more preferably 30,000 to 500,000, still more preferably 50,000 to 400,000.
  • both the intrinsic viscosity [ ⁇ ] and the weight average molecular weight (Mw) of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention are in the above-described ranges.
  • the non-conjugated polyene (C) include VNB, and it is more preferable that the non-conjugated polyene (C) be VNB. That is, in the above-described Formulae (1) and (2), Formula (4) as described later and the like, "weight fraction of (C)" is preferably "weight fraction of VNB" (wt%).
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention contain, in addition to structural units derived from the compounds (A), (B) and (C), structural units derived from the non-conjugated polyene (D) containing per molecule only one partial structure selected from the group consisting of the structures of the above general formulae (I) and (II), with the non-conjugated polyene (D) content being 0 wt% to 20 wt% in terms of a weight fraction (where the total weight fraction of the compounds (A), (B), (C) and (D) is 100 wt%).
  • the Formula (4) specifies the content of the non-conjugated diene (total of (C) and (D)) per molecule of the copolymer.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) containing structural units derived from the non-conjugated polyene (D) satisfy the Formula (4) because a hydrosilyl-crosslinked molded article obtained from the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) composition has excellent mechanical properties and heat aging resistance.
  • Log ⁇ * ⁇ 0.01 /
  • Log ⁇ * ⁇ 10 ⁇ 0.0753 ⁇ apparent iodine value derived from non-conjugated polyene C + 1.42
  • the left side member represents shear rate dependency giving an index of the amount of long-chain branching
  • the right side member represents an index of the content of non-conjugated polyene (C) which has not been consumed as long-chain branches during polymerization. It is preferable that the requirement (vii) and the above Formula (5) be satisfied because the degree of long-chain branching is not excessively high. On the other hand, when the above Formula (5) is not satisfied, it is apparent that the ratio of non-conjugated polyene (C) consumed for formation of long-chain branches to copolymerized non-conjugated polyene (C) is high.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention contain a sufficient amount of structural units derived from the non-conjugated polyene (C), and it is preferable that the weight fraction of structural units derived from the non-conjugated polyene (C) (weight fraction of (C) (wt%)) in the copolymer, and the weight average molecular weight (Mw) of the copolymer satisfy the following formula (6). 6 ⁇ 0.45 ⁇ Ln Mw ⁇ weight fraction of C ⁇ 10
  • the number of structural units derived from the non-conjugated polyene (C) represented by (n C ), per weight average molecular weight (Mw), is preferably 6 or more, more preferably 6 or more and 40 or less, still more preferably 7 or more and 39 or less, furthermore preferably 10 or more and 38 or less.
  • Such an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) contains a sufficient amount of structural units derived from the non-conjugated polyene (C) such as VNB, has a low content of long-chain branches, is excellent in curing properties in crosslinking performed using a peroxide, has good moldability, and is excellent in balance of physical properties such as mechanical properties, and particularly excellent in heat aging resistance.
  • the number of structural units derived from the non-conjugated polyene (D) which represented by (n D ), per weight average molecular weight (Mw), is preferably 29 or less, more preferably 10 or less, still more preferably less than 1.
  • Such an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention is preferable because the content of structural units derived from the non-conjugated polyene (D) such as ENB is reduced to the extent that the purpose of the present invention is not hindered, post-crosslinking hardly occurs, and sufficient heat aging resistance is exhibited.
  • the number of structural units derived from the non-conjugated polyene (C) represented by (n C ) or the number of structural units derived from the non-conjugated polyene (D) represented by (n D ), per weight average molecular weight (Mw), in the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) can be determined in accordance with the following formulae from the molecular weight of the non-conjugated polyene (C) or (D), the weight fraction of structural units derived from the non-conjugated polyene (C) or (D) in the copolymer (weight fraction of (C) or (D) (wt%)) and the weight average molecular weight (Mw) of the copolymer.
  • n C Mw ⁇ weight fraction of C / 100 / molecular weight of non-conjugated polyene
  • C n D Mw ⁇ weight fraction of D / 100 / molecular weight of non-conjugated polyene D
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) is a copolymer obtained by copolymerizing a monomer including ethylene (A), the ⁇ -olefin (B) having 3 to 20 carbon atoms, the non-conjugated polyene (C) containing per molecule a total of two or more partial structures each selected from the group consisting of the structures of the above general formulae (I) and (II), and optionally the non-conjugated polyene (D) containing per molecule a total of only one partial structure selected from the group consisting of the structures of the above general formulae (I) and (II).
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention may be produced by any method as long as the requirements (i) to (v) are satisfied, and the copolymer (S) is preferably one obtained by copolymerizing monomers in the presence of a metallocene compound, more preferably one obtained by copolymerizing monomers in the presence of a catalyst system containing a metallocene compound.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S) according to the present invention can be produced by employing, for example, a method using a metallocene catalyst as described in International Publication No. WO 2015/122495 .
  • the hydrosilyl group-containing compound (Y) acts as a crosslinking agent by reacting with a polymer having a terminal double bond, such as an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S).
  • a polymer having a terminal double bond such as an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S).
  • S ethylene/ ⁇ -olefin/non-conjugated polyene copolymer
  • the hydrosilyl group-containing compound (Y) has been produced and commercially available.
  • the structure of the hydrosilyl group-containing compound (Y) is not limited, and for example, any of resinous materials of linear, cyclic and branched structures or three-dimensional network structure, which have been heretofore produced and sold, can be used, and the hydrosilyl group-containing compound (Y) for use in the present invention is required to contain at least two hydroxyl groups per molecule.
  • hydrosilyl group-containing compound (Y) typically a compound represented by the following general composition formula may be used.
  • R 4 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, where an aliphatic unsaturated bond is not included.
  • the monovalent hydrocarbon group include alkyl groups ranging from a methyl group or ethyl group to a nonyl group or decyl group and including isomers such as n-, iso-, sec- and tert-alkyls; phenyl groups; and halogen-substituted alkyl groups such as a trifluoropropyl group.
  • a methyl group, an ethyl group, a propyl group, a phenyl group and a trifluoropropyl group are preferable, with a methyl group being especially preferable.
  • b satisfies 0 ⁇ b ⁇ 3, preferably 0.6 ⁇ b ⁇ 2.2, particularly preferably 1.5 ⁇ b ⁇ 2, and c satisfies 0 ⁇ c ⁇ 3, preferably 0.002 ⁇ c ⁇ 2, particularly preferably 0.01 ⁇ c ⁇ 1, and b + c satisfies 0 ⁇ b + c ⁇ 3, preferably 1.5 ⁇ b + c ⁇ 2.7.
  • the hydrosilyl group-containing compound (Y) is an organohydrogenpolysiloxane in which the number of silicon atoms per molecule is preferably 2 to 1000, especially preferably 2 to 300, most preferably 4 to 200.
  • Specific examples thereof include siloxane oligomers such as 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane and 1,3,5,7,8-pentamethylpentacyclosiloxane, methylhydrogenpolysiloxanes blocked at both molecular chain terminals by trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymers blocked at both molecular chain terminals by trimethylsiloxy groups, methylhydrogenpolysiloxanes blocked at both molecular chain terminals by silanol groups, dimethylsiloxane-methylhydrogensiloxane copolymers blocked at both molecular chain terminals by
  • Examples of the methylhydrogenpolysiloxanes blocked at both molecular chain terminals by trimethylsiloxy groups include compounds represented by the following formula, and compounds represented by the following formula with the proviso that some or all of methyl groups are replaced by ethyl groups, propyl groups, phenyl groups, trifluoropropyl groups or the like.
  • Examples of the dimethylsiloxane-methylhydrogensiloxane copolymers blocked at both molecular chain terminals by trimethylsiloxy groups include compounds represented by the following formula, and compounds represented by the following formula with the proviso that some or all of methyl groups are replaced by ethyl groups, propyl groups, phenyl groups, trifluoropropyl groups or the like.
  • Examples of the methylhydrogenpolysiloxanes blocked at both molecular chain terminals by silanol groups include compounds represented by the following formula, and compounds represented by the following formula with the proviso that some or all of methyl groups are replaced by ethyl groups, propyl groups, phenyl groups, trifluoropropyl groups or the like.
  • Examples of the methylhydrogenpolysiloxanes blocked at both molecular chain terminals by dimethylhydrogensiloxy groups include compounds represented by the following formula, and compounds represented by the following formula with the proviso that some or all of methyl groups are replaced by ethyl groups, propyl groups, phenyl groups, trifluoropropyl groups or the like.
  • Examples of the dimethylsiloxane-methylhydrogensiloxane copolymers blocked at both molecular chain terminals by dimethylhydrogensiloxy groups include compounds represented by the following formula, and compounds represented by the following formula with the proviso that some or all of methyl groups are replaced by ethyl groups, propyl groups, phenyl groups, trifluoropropyl groups or the like.
  • the above compounds can be produced by a known method.
  • such a compound can be easily obtained in the following manner: octamethylcyclotetrasiloxane and/or tetramethylcyclotetrasiloxane are equilibrated at a temperature of about -10°C to +40°C in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid with a compound containing a triorganosilyl group or a diorganohydrogensiloxy group such as hexamethyldisiloxane or 1,3-dihydro-1,1,3,3-tetramethyldisiloxane which can be a terminal group.
  • a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid
  • a compound containing a triorganosilyl group or a diorganohydrogensiloxy group such as hexamethyldisi
  • the amount of the hydrosilyl group-containing compound (Y) according to the present invention is typically 0.1 to 100 parts by weight, preferably 0.1 to 75 parts by weight, more preferably 0.1 to 50 parts by weight, still more preferably 0.2 to 30 parts by weight, furthermore preferably 0.2 to 20 parts by weight, especially preferably 0.5 to 10 parts by weight, most preferably 0.5 to 5 parts by weight based on 100 parts by weight of a polymer having a terminal double bond, preferably the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S).
  • Use of the hydrosilyl group-containing compound (Y) in an amount of more than 100 parts by weight is not preferable because cost efficiency is deteriorated.
  • the platinum-based catalyst (Z) for hydrosilicon crosslinking for use in the present invention is an addition reaction catalyst, and may be used without being particularly limited as long as the platinum-based catalyst promotes addition reaction of an alkenyl group of a polymer having a terminal double bond, preferably the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S), with a hydrosilyl group of the hydrosilyl group-containing compound (Y) (hydrosilylation reaction of alkene).
  • the specific platinum-based catalyst may be a known platinum-based catalyst which is typically used for curing of addition curing type, and examples thereof include a fine powder metal platinum catalyst as described in U.S. Patent No. 2,970,150 , a platinic chloride catalyst as described in U.S. Patent No. 2,823,218 , a complex compound of platinum with a hydrocarbon as described in U.S. Patent Publication No. 3,159,601 and U.S. Patent No. 159,662 , a complex compound of chloroplatinic acid with an olefin as described in U.S. Patent No. 3,516,946 , and a complex compound of platinum with vinylsiloxane as described in U.S. Patent No. 3,775,452 and U.S. Patent No. 3,814,780 .
  • platinum-based catalyst More specific examples of the platinum-based catalyst include elemental platinum (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, or carriers of alumina, silica or the like with a platinum carrier carried thereon.
  • the platinum-based catalyst (Z) for hydrosilicon crosslinking is used in an amount of typically 0.1 to 100000 ppm by weight, 0.1 to 10000 ppm by weight, more preferably 1 to 5000 ppm by weight, especially preferably 5 to 1000 ppm by weight based on the amount of a polymer having a terminal double bond, preferably the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S).
  • S ethylene/ ⁇ -olefin/non-conjugated polyene copolymer
  • the platinum-based catalyst (Z) for hydrosilicon crosslinking is used in an amount within the above-described range, it is possible to obtain an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer composition which enables formation of a crosslinked molded article having a moderate crosslinking density, and an excellent strength property and elongation property.
  • the reaction inhibitor (D) for use in the present invention inhibits crosslinking reaction (hydrosilylation addition reaction to alkene) of an alkenyl group of a polymer having a terminal double bond, preferably the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S), with a hydrosilyl group of the hydrosilyl group-containing compound (Y). Inhibition of the crosslinking reaction is required for stabilizing processability during kneading and molding.
  • reaction inhibitor (D) for use in the present invention examples include benzotriazole, ethynyl group-containing alcohols (e.g. ethynylcyclohexanol), acrylonitrile, amide compounds (e.g.
  • the reaction inhibitor (D) is used in an amount of typically 0.05 to 5 parts by weight, preferably 0.07 to 5 parts by weight, more preferably 0.07 to 4.5 parts by weight, still more preferably 0.1 to 4.5 parts by weight, especially preferably 0.1 to 3.0 parts by weight, most preferably 0.1 to 1.0 parts by weight based on 100 parts by weight of a polymer having a terminal double bond, preferably the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S).
  • the crosslinking rate may be excessively high, and when the reaction inhibitor (D) is used in an amount of more than 5 parts by weight, crosslinking may hardly occur due to an increased reaction inhibition effect.
  • a reinforcing agent such as a reinforcing agent, an inorganic filler, a softening agent, an anti-aging agent (stabilizer), a processing aid, a foaming agent, a foaming aid, a plasticizer, a colorant, other rubber compounding agents, rubber and resin
  • a reinforcing agent such as a reinforcing agent, an inorganic filler, a softening agent, an anti-aging agent (stabilizer), a processing aid, a foaming agent, a foaming aid, a plasticizer, a colorant, other rubber compounding agents, rubber and resin
  • the type and the content of each of the compounding agents are appropriately selected according to a use purpose, and among these agents, a reinforcing agent, an inorganic filler, a softening agent and the like are particularly preferably used.
  • examples of the resin which is optionally used include general-purpose resins such as polyethylene, polypropylene and polystyrene.
  • the rubber which is optionally used silicone rubber, ethylene/propylene random copolymer rubber (EPR), natural rubber, styrene/butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber and the like may be compounded.
  • Rubber (EPT) which is different from but similar to the copolymer (A) may be used, or even two or more of the copolymers (A) may be used in mixture as long as the copolymers (A) have different iodine values, intrinsic viscosities [ ⁇ ] or molar ratios of ethylene to the ⁇ -olefin having 3 to 20 carbon atoms.
  • a component having a low intrinsic viscosity and a component having a high intrinsic viscosity may be mixed.
  • the polymer composition according to the present invention is a composition containing a polymer having a terminal double bond, preferably the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S), the hydrosilyl group-containing compound (Y), the platinum-based catalyst (Z) and the reaction inhibitor (D).
  • the preferred amount of each component present in the polymer composition according to the present invention is as described above.
  • the method for producing a crosslinked molded article according to the present invention is a method for producing a molded article, including melt-kneading the polymer composition according to the present invention at a temperature in the range of typically 50 to 130°C, preferably 70 to 110°C, subjecting the polymer composition to injection molding in a mold set at a temperature in the range of typically 90 to 220°C or 100 to 200°C, preferably 110 to 190°C, performing first-stage crosslinking (primary crosslinking) in the mold, subsequently removing the injection-molded article from the mold, and then performing second-stage crosslinking (secondary crosslinking) in a heat medium or the like.
  • the time of the primary crosslinking performed in the mold is typically 0.5 to 60 seconds, preferably 0.6 to 40 seconds, more preferably about 0.7 to 20 seconds.
  • the temperature of the heat medium is typically 90 to 220°C, preferably 100 to 200°C, and the time of the secondary crosslinking (time of heating in the heat medium) is typically 5 to 120 minutes, preferably 10 to 60 minutes.
  • primary crosslinking is performed in a short time as described above, and thus the time of crosslinking in the mold can be reduced, so that the cycle of injection molding can be shortened to enhance production efficiency.
  • a predetermined amount of a polymer having a terminal double bond preferably the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S), etc. may be weighed and fed into an extruder of an injection molding machine, and then melt-kneaded at a temperature in the above-described range, or alternatively, a predetermined amount of a polymer having a terminal double bond, preferably the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (S), etc. may be weighed, then melt-kneaded beforehand using a Banbury mixer, a kneader, or an internal mixer such as Inter Mix, and put in an injection molding machine.
  • the method for performing secondary crosslinking of a molded article in the method for producing a molded article according to the present invention can be carried out using, for example, hot air, a glass bead fluidized bed, an UHF (ultrahigh frequency electromagnetic wave), steam, or a heating-type crosslinking bath such as a LCM (thermally molten salt bath). It is preferable that heating in the secondary crosslinking be performed at a relatively low rate using a heat medium such as heated air or heated water vapor in an oven or the like because crosslinking is apt to evenly progress, so that the difference between the crosslinking density of the surface part and the crosslinking density of the inner part of the crosslinked molded article can be controlled to be small.
  • a heat medium such as heated air or heated water vapor in an oven or the like because crosslinking is apt to evenly progress, so that the difference between the crosslinking density of the surface part and the crosslinking density of the inner part of the crosslinked molded article can be controlled to be small.
  • the secondary crosslinking process may be a batch-type process or a continuous-type process.
  • a radiation such as light, a ⁇ -ray or an electron beam may be applied at the time of performing heating.
  • secondary crosslinking is performed, and thus without being held in the mold for a long time, the crosslinked molded article can be evenly crosslinked to the inner part, so that it is possible to obtain a crosslinked molded article having a small difference in crosslinking density between the central part and the surface part of the molded article.
  • the crosslinked molded article according to the present invention includes the polymer composition described above, and preferably satisfies the following requirement (I).
  • the crosslinked molded article of the present invention satisfies the following relational Formula (7').
  • the center of the crosslinked molded article means a point which is the farthest from a mold contacting surface during primary crosslinking.
  • the center is on the surfaces formed by dividing the article in a thickness direction into two equal parts.
  • the plate-shaped crosslinked molded article is divided in a thickness direction into three equal parts: a surface part/an inner part/a surface part, it is preferable that the crosslinking density (A) of the surface parts and the crosslinking density (B) of the inner part satisfy the above relational Formula (7), more preferably the above relational Formula (7').
  • the crosslinked molded article of the present invention has a very small difference in crosslinking density between surface parts and the inner part, and has uniform and stable mechanical properties, and particularly small compression set.
  • the crosslinked molded article of the present invention are suitably used for hoses, tire rubber, O-rings, industrial rolls, packings (e.g. capacitor packings), gaskets, rubber cushions, vibration-proof materials or damping materials (e.g. engine mounts and motor mounts), muffler hangers, sponges (e.g. heat insulation sponges, protecting sponges and slightly foamed sponges), color skin materials, sheet feeding rolls and the like, for example.
  • the crosslinked molded article is suitably used particularly for automobile interior and exterior components, and applications in which heat resistance is required, and the crosslinked molded article is suitable for hoses, O-rings, packings, sponges, rubber cushions, and sponges.
  • the weight fraction (wt%) of each structural unit and the molar ratio of ethylene/ ⁇ -olefin in the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer were determined from values measured by 13 C-NMR.
  • the intrinsic viscosity [ ⁇ ] (dl/g) was measured at a temperature of 135°C with decalin as a measurement solvent using a full-automatic intrinsic viscosity meter manufactured by Rigo Co., Ltd.
  • the weight average molecular weight (Mw), the number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn) are polystyrene-equivalent values measured by gel permeation chromatography (GPC).
  • the measurement apparatuses and conditions are as follows. The molecular weight was calculated on the basis of a conversion method with a standard curve prepared using commercially available monodisperse polystyrene.
  • VNB 5-vinyl-2-norbornene
  • hexane As a polymerization solvent, hexane was used (feeding rate: 23.6 L/h). Ethylene, butene, VNB and hydrogen were continuously supplied to the polymerization vessel at feeding rates of 4.5 kg/h, 14.4 kg/h, 420 g/h and 40.0 NL/h, respectively.
  • Di(p-tolyl) methylene(cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dichloride as a main catalyst was continuously supplied to the polymerization vessel at a feeding rate of 0.0052 mmol/h while the polymerization pressure and the polymerization temperature were maintained at 1.65 MPaG and 95°C, respectively.
  • (C 6 H 5 ) 3 CB(C 6 F 5 ) 4 (CB-3) as a cocatalyst and triisobutylaluminum (TIBA) as an organoaluminum compound were continuously supplied to the polymerization vessel at feeding rates of 0.026 mmol/h and 20 mmol/h, respectively.
  • the ethylene/butene/VNB copolymer (S-1) formed from ethylene, butene and VNB was obtained at a rate of 6.0 kg per hour.
  • the hardness (Type A Durometer, HA) of the crosslinked sheet was measured using six 2 mm crosslinked sheets each having a smooth surface, where the flat parts of the crosslinked sheets were stacked to a thickness of about 12 mm. It is to be noted that specimens having contaminants, bubbles or scratches were not used. The specimen had a dimension allowing the measurement to be performed with a press needle tip end positioned at a distance of 12 mm or more from the end of the specimen.
  • JIS K 6251 a tensile test was conducted under the condition of a measurement temperature of 23°C and a tensile speed of 500 mm/min to measure the strength at break (TB) [MPa] and the elongation at break (EB) [%] of the sheet. Specifically, a sheet-shaped crosslinked molded article was punched to prepare a No. 3 dumbbell specimen as described in JIS K 6251 (2001).
  • the specimen was subjected to a tensile test under the condition of a measurement temperature of 25°C and a tensile speed of 500 mm/min to measure the tensile stress at break (TB) and the tensile elongation at break (EB).
  • the crosslinking density v was calculated from the following Flory-Rehner formula (a) incorporating equilibrium swelling.
  • V R in the formula (a) was determined by swelling and extracting the crosslinked 2 mm sheet with toluene under the condition of 37°C and 72 hours.
  • the surface crosslinking density (A) and the inner part crosslinking density (B) were determined in the following manner.
  • a crosslinked molded article sheet prepared with a thickness of 2 mm was divided in a cross-sectional direction into three parts to obtain three 0.67 mm-thick sheets (two outer sheets and one inner sheet), and the surface part crosslinking density (A) and the inner part crosslinking density (B) were similarly measured using the outer sheets and the inner sheet, respectively.
  • Samples of 20 ⁇ 20 mm were prepared, and five of the samples were stacked to obtain a specimen.
  • the total height of five samples each subjected to dimension measurement was set to a sample height, and the specimen was compressed by 25% with respect to the height (about 10 mm) of the specimen before application of a load, set together with a compression plate holding tool in an oven at a specified temperature, and heat-treated for a specified time. Subsequently, the specimen was released, and allowed to cool for 30 minutes, the height of the specimen was then measured, and the compression set (%) was calculated from the following calculation formula.
  • compression set % t ⁇ ⁇ t 1 / t ⁇ ⁇ t 2 ⁇ 100
  • the obtained compound was subjected to press crosslinking at 180°C for 20 minutes to obtain a flat plate-shaped crosslinked molded article of 150 ⁇ 150 ⁇ 2 mm.
  • Table 2 shows the physical properties of the obtained crosslinked molded article.
  • the compound obtained in the first stage was wound around a 8 inch roll (manufactured by Nippon Roll MFG. Co., Ltd.) (surface temperature of front roll: 50°C, surface temperature of rear roll: 50°C, the rotation speed of the front roll: 16 rpm and the rotation speed of the rear roll: 18 rpm).
  • a flat plate mold of 150 ⁇ 150 ⁇ 2 mm was attached to a 75 t vertical injection (VI-75P(B)-40/60SPR5(500)-P manufactured by Matsuda Seisakusho Co., Ltd.), and injection molding was performed under the condition of a nozzle temperature of 90°C, a mold temperature of 180°C, an injection rate of 40 cm 3 /sec, a mold clamping pressure of 135 kgf and a varied vulcanization time (as shown in Table 1).
  • the primary-crosslinked molded article obtained by the injection molding was subjected to secondary crosslinking at 180°C for 30 minutes using a gear oven (product name: Temperature Chamber with Rotating Specimen Rack (Gear Oven), model: GPH-201, maker: ESPEC Corp.).
  • the obtained crosslinked molded articles each had a good appearance.
  • Table 2 shows the physical properties of the crosslinked molded articles.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
EP18892394.0A 2017-12-18 2018-12-13 Corps moulé réticulé, et procédé de fabrication de celui-ci Pending EP3730554A4 (fr)

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PCT/JP2018/045938 WO2019124223A1 (fr) 2017-12-18 2018-12-13 Corps moulé réticulé, et procédé de fabrication de celui-ci

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JP7355550B2 (ja) * 2019-08-08 2023-10-03 三井化学株式会社 燃料電池用ガスケット
JP7481969B2 (ja) 2020-09-07 2024-05-13 三井化学株式会社 ゴム組成物およびその用途

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KR20200087234A (ko) 2020-07-20
US11613594B2 (en) 2023-03-28
JPWO2019124223A1 (ja) 2020-11-19
WO2019124223A1 (fr) 2019-06-27
US20210179752A1 (en) 2021-06-17
CN111479877A (zh) 2020-07-31
EP3730554A4 (fr) 2021-09-01

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